Fluorescent hydrocarbon oils



Patented Mar. l6, 1937 FLUORESCENT nrnRocAnnoN oms John"M. Tinker,- South Milwaukee, and Viktor Wemmayr,

Milwaukee, Wis.,. assignors to E. I. 'du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing,

This invention relates to the' coloring of hydrocarbon oils and other hydrocarbon'type so]- a strong fluorescence.

In the distillation ofmany petroleum hydro-' carbons for the preparation of the various 'frac- 20 duce fluorescent hydrocarbon oils and other sol- 25 solved in hydrocarbon oils or other hydrocarbon 30 shades a variety of colors, so'that those manu 3 5 matic ketones. of the anthraquinone series, such 40 with a reducing metal, for example, iron, zinc,

300 and 360 C., the upper limit being fixed by 0., with optimum. results being obtained at temperatures between Application November 21, 1934, Serial N 754,086

copending application Serial No. 754,085 filed November 21, 1934.

We have found that high boiling solvents may the reaction is carried out modify to some extent the shade of the resulting product. Those high boiling solvents which boil above 280 C. in genera] are suitable so long as they do into the reaction to materially alter the formation and/or methyl-substituted benzoyl 2 benzoic acids have been found to operate satisfactorily The benzoyl-bento have an appreciable eflect on the preparation of the reaction and not due to any combination of the solvent with the-anthraquinone body. The reaction may also be carried out with lower boiling solvents where elevated pressure is used.

Any of the metals which under the conditions of'the reaction will efiect a reduction of the anthraquinone compounds may be employed, such as zinc, iron, nickel, tin, lead, etc.; and for convenience these metals will be referred to as reducing metals. I

The following examples are given to more fully illustrate our invention. The parts used are by weight.

Example 1 100 parts of benzanthrone are melted and heated to 250 C. 80 parts of iron powder are added black reaction mass is poured 'onto pans to cool distilled oil or removed with steam. This prodof solvent insoluble material, can be used in place of a more pure benzanthrone without affecting as Example 2 120 parts of benzanthrone are heated to about 250 with 80 parts of benzophenone, and 100 parts of iron powder are added The mass is'then heated to the reflux tempera-- ture of the benzophenone and held there for about 20 hours. Some of the benzophenone may be recovered by raising the temperature above its boiling point. The recovered benzophenone may be used for subsequent preparation without further purification. The resulting compound may be isolated by the method described in Example 1, or the mass can be cooled almost to its melting point and a high boiling solvent, such as dichlorobenzene or trichlorobenzene, can be added. The green bloom producing agent dissolved in these solvents is then isolated by distilling off the solvent. The product shows a cence in hydrocarbon oils.

Example 3 150 parts of benzanthrone, 50 parts of 'benzoyl- Example 4 750 parts of benzanthrone and 250 parts of be zoyl-2-benzoic acid are heated to about 250 C. and 650 parts of iron powder are slowly added at this temperature. The mixture is then heated to 320-330 C. for about 24 hours. Some dark colored oil formed during the reaction may be distilled ofi. The charge is worked up as described in the previous examples. The compound, which imparts to liquid hydrocarbons a strong green fluorescence, is very soluble in organic solvents, such as benzene, gasoline, kerosene, parafiln oil, pyridine, and others, showing bright green fluorescence in dilute solutions. It is sparingly soluble in alcohol, acetic acid, and acetic anhydride. The product, when isolated as described above, has a meltingpoint of about 198210 C. A combustion shows it contains 94.65% carbon and 5.3% hydrogen. It has a melting point of 239- 249 C. after two crystallizations from pyridine, and analyzes 95.3% carbon and 4.26% hydrogen. The purified product has the same fluorescence as the crude product. It is soluble in cold sulfuric acid with blue color and red fluorescence. It can 'easily be oxidized to vat dyes. Compounds with similar green fluorescence can be obtained from other benzanthrones, and other benzoyl-2-benzoic acids may be used as the solvents, as illustrated by the following examples.

Example 5 '15 parts of 2-methyl-benzanthrone and 40 parts of iron powder are heated to 300 C. for several hours. A product which exhibits yellow-green fluorescence in solvents and hydrocarbon oils is obtained by extracting the crude 7 fusion mass obtained.

at this temperature.

light green fluores- Example 6 50 parts of Bzl-chloro-benzanthrone, 20 parts of benzoyl-Z-benzoic acid, and 40 parts of iron are heated to 310 C. for a few hours. A product showing a yellow-green bloom in solvents and hydrocarbon oils can be isolated in the manner above described.

Example 7 150 parts of benzanthrone, 50 parts of alphanaphthoyl-Z-benzoic acid powder are heated to 300-330 -C. for 24 hours. The finished reaction mass is cooled to about 200 C. and ortho-dichlorobenzene is added to it. The whole is then extracted with dichlorobenzene and the product is isolated by steam distilling oi? the solvent. A product exhibiting a yellow-green fluorescence in solvents and hydrocarbon oils is obtained with good yield.

Products showing a similar fluorescence are formed when benzanthrone and iron powder are heated with 4'-methy1- or 4-chloro-benzoyl-2- benzoic acid or mixtures thereof.

Example 8 225 parts of benzanthrone and '75 parts of benzoyl-2-benzoic acid are heated with 195 parts of zinc dust to 310 C. for 17 hours. The crude product is extracted and a product which exhibits a yellow-green fluorescence in solvents is obtained.

Example 9 20 parts of 1,1'-dianthraquinonyl, 40' parts of benzoyl-2-benzoic acid, 40 parts of benzophenone and 20 parts of iron powder are heated to 310- 320 for 20 hours. A product which exhibits an olive-green fluorescence in solvents and hydrocarbon oils is obtained by the usual extraction.

Example 10 1000 parts of anthraquinone, 250 parts of benzoyl-2-benzoic acid, and parts of benzophenone are heated to 260 C. and 600 parts of iron powder are added slowly at this temperature. The temperature is then raised to 310 and maintained there for about 18 hours. The dark reaction product is poured onto pans and milled after cooling. The red fluorescent compound is separated from the iron residue-by extraction with hot solvent naphtha and isolated by steam distilling off the solvent. 662 parts of dry product are obtained. This compound shows a strong red fluorescence when added to organic solvents or hydrocarbon oils in small amounts.

A product showing a similar, but much weaker fluorescence, is obtained when anthraquinone alone is heated with iron powder to 300-360 C.

Example 11 powder, which shows a yellow-red fluorescence in dilute solutions in organic solvents and hydrocarbon oils. The melting point of the product as obtained is about -208 C. It contains 86.33% carbon;5% hydrogen and 8.67% oxygen. It contains some unchanged anthraquinone which does and '15 parts of iron benzanthrone, anthraquinone,

as a bloom producing agent for The solution in sulfuric acid not afi'ect its use hydrocarbon oils.

is yellow-brown with a strong yellow fluorescence.

finished fusion Example 12 200 parts of benzanthrone, 60 parts of 1,4- dihydroxy-anthraquinone and 100 parts of iron powder are heated to 330 C. for-22 hours. A product with a yellow gre n bloom is obtained by extraction.

small amounts of benzophenone to 310 A and benzoyl-2-benzoic acid or Example 14 Equal parts of benzanthrone, 2 -chloro-anthraquinone and iron are heated in the presence of A product which exhibits red fluorescence in solvents and oils is by the usual method of isolation.

Example 15 a yellow obtained 150 parts of anthraquinone, 100 parts of abietene, and 50 parts of benzanthrone are heated to 340 for 24-hours in the presence of 100 parts obtained when benzanthrone, 4'-chloro-benzoyl- -2-benzoic acid and iron powder or anthraquinone and iron powder are heated with abietene or with abietane. I

Example 16 100 parts of benzanthrone, 100 parts of anthraquinone and 100 parts of tin are heated to Example 17 benzanthrone, anthraquinone heated to 310 for 20 hours, some benzophenone.

Equal parts of and zinc dust are inthe presence of Compounds giving a yellow red to bluish red anthanthrone, anthanthrone pyrazolanthrone' and benzoyl-2-benzoic acid are heated with reducing metals in the manner described in the preceding examples.

The formation of these compounds b zomes noticeable during the first hour of heating at temperatures above 290 C. with optimum refrom the color compound whendissolved in oil; too small amounts of the metal give dull shades- The time required to complete the reaction is also materially increased whentoo small an amount of metal is used.

Numerous variations in the processes above described may be made without departing from the anthraquinone series.

The amounts of our bloom producing color bodthe particular the oil naturally exhibits.

By using small amounts of the green or the hydrocarbon oil. By the term "hydrocarbon oil from the lightest naphtha fractions lubricating oils and to the crude oil We claim:

consisting of iron, nickel and lead for an extended period at temperatures above 280 C. but below 360 C. under conditions which prevent the escape of any material amount of the reaction products.

yellow-green fluorescence which comprises dissolving therein a color compound obtained by heating benzanthr'one with a reducing metal of the class consisting of iron, zinc, tin, nickel and lead for an extended period at temperatures above 280 C. but below 360 C. under conditions which prevent the escape of any material amount of the reaction products.

3. A process for producing hydrocarbon oils and hydrocarbon type solvents having an orange to red fluorescence which comprises dissolving nickel and lead for an extended period at temperatures above 280 C. but below 360 C. under conditions which prevent the escape of any material amount of the reaction products.

6. Hydrocarbon oils and hydrocarbon type solvents containing as an added ingredient a fluorescence exhibiting color component the product obtained by heating a benzanthrone with a reducing metal-of the class consisting of iron,

therein a color compound 'obtained by heating zinc, tin, nickel and lead for an extended period 10 anthraquinone with a reducing metal of the class at temperatures above 280 C. but below 360 C. consisting of iron, zinc, tin, nickel and lead for under conditions which prevent the escape of an extended period at temperatures above 280 any material amount of the reaction products, C. but below 360 C. under conditions which pre- '7. Hydrocarbon oils and hydrocarbon type vent the escape of any material amount of the solvents containing as an added e nt a reaction products. fluorescence exhibiting color component the 4. A process for producing hydrocarbon oils product obtained by heating anthraquinone with and hydrocarbon type solvents having an orange a reducing metal of the class con ng f i to red fluorescence which comprises dissolving Zinc, tin, nickel and lead an extended Period therein a color compound obtained by heating a at temperatures above 280 C. but below 360 C. mixture of benzanthrone and anthraquinone under conditions which prevent the escape of any with a reducing metal of the class consisting of material amount of the reaction products iron, zinc, tin, nickel and lead for an extended 8. Hydrocarbon oils and hydrocarbon type period at temperatures above280 C. but below solvents containing as an added ingredient a 360 C. under conditions which prevent the fluorescence exhibiting color component the escape of any material amount of the reaction product obtained by heating a mixture of benzproducts. anthrone and anthraquinone with a reducing 5. Hydrocarbon oils and hydrocarbon type metal of the class consisting of iron, zinc, tin, solvents containing as an added ingredient a nickel and lead for an extended period at temfluorescence exhibiting color component the peratures above 280 C. but below 360 C. under conditions which prevent the escape of any material amount of the reaction products.

product obtained by heating a polynuclear ketone of the class consisting of anthraquinone, benzanthrone and anthanthrone, and their methyl and halogen derivatives, with a reducing metal of the class consisting of iron, zinc, tin,

JOHN M. TINKER. VIKTOR. M. WEINMAYR.

CERTIFICATE OF CORRECTION.

Patent No. 2,074,288. March 16, 1937 JOHN M. TINKER, ET AL.

It is hereby certified that error of the above numbered patent requiri first column, line 36, for the word "an" read and; and second column, line 13. for "benzo12benzoic" read benzoyl-Z-benzoic; page 2, second column .line 66, for "napththa" read naphtha; and that the said Letters Pat nt should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 1st day of June, A. D. 1937.

appears in the printed specification ng correction as follows: Page 1,

Henry Van Arsdale (Seal) Acting Commissioner of Patents. 

